Cellular phenol aldehyde plastic resins



United States Patent Eli Simon, Los Angeles, and Frank W. Thomas, Burbank,

Califi, assignors to Lockheed Aircraft Corporation, Burbank, Calif.

No Drawing. Application August 6, 1952, Serial No. 302,996

14 Claims. (Cl. 260-25) This invention relates to new and useful products in the nature of foamed synthetic resins and relates more particularly to cellular phenol-aldehyde resins and to methods of making the same.

Cellular phenolic resin products were introduced prior to our invention but so far as we are aware these earlier products could not be produced satisfactorily in large sections or masses. When attempts were made to foam or cast these products in large and relatively large monolithic sections, the cell structure was irregular and unsatisfactory. In most instances excessively large voids were formed in the material, weakening it and making it unsuitable for many applications. This non-uniformity in cell structure and, therefore, in strength and insulating characteristics, resulted from the excessively rapid rate of gas evolution and polymerization of the resin during the foaming reaction. When the rate of reaction is excessively rapid the walls of the gas-filled cells become thin at the regions of mutual contact of the cells and the continuing evolution of the gas ruptures the cells before the resin has polymerized sufficiently to resist such rupture, the rupturing of the cells being progressive so that large voids or pockets are left in the material or product. Although this action is more pronounced in large masses or sections, it also occurs in smaller pours or masses where the rate of reaction of the reactant mixture is uncontrolled and too rapid.

It is an object of the present invention to provide low density foamed or cellular phenolic resin products that are substantially uniform in cell structure. The products of the invention have substantially uniform cells throughout and do not have the overly large voids or cells which have characterized the earlier phenolic resin foams.

It is another object of the invention to provide for the pouring or casting of cellular phenolic resin products in large and relatively large masses or sections without the development of excessively large voids therein. A

Another object of the invention is to provide foaming compositions and a method for producing cellular phenolic products of selected cell size, density, etc, In accordance with the present invention the rate of reaction of the foam producing reactant mixture is controlled so as to permit the ready manufacture of phenolic resin foams of varied and selected characteristics, cell sizes and composition, the slow or controlled rate of reaction permitting the use of preferred and selected concentrations of constituents and constituents or ingredients for obtaining foamed or cellular products of substantially different and desired physical characteristics Without the creation of large voids, discontinuities or excessive irregularity of cell structure.

, Another object of the invention is to provide foaming phenolic resin compositions that react slowly and in a controlled manner to facilitate pouring, spreading, workingtand handling and that produce cellular products of generally uniform cell structure throughout. The foaming compositions of the invention are 'characterizedby ice novel catalysts in combination with gassing agents, such as divided aluminum and the like. The foamed or cellular materials are the products of mutual or dual reactions; that is (1) an initial reaction between a special acid catalyst and a selected gassing agent such as a divided metal, and (2) a second reaction occurring during the first and increasing the chain length of the phenol alcohols formed during reaction of the resol type phenolic resins employed in the composition, the chain length growing at a controlled or slow rate as a result of the acid blend constituting the catalyst, one acid serving to reduce or slow down the rate of reaction of the other. The nature of the blend of acids, and the diluent, which may be incorporated in the catalyst, together withthe character of the gassing agent contribute to the controlled foaming reaction of the reactant phenolic resin mass to produce a product having uniform cell structure throughout even in large sections and distinguishing from prior products of this general character wherein the reaction is uncontrolled and the product is non-uniform in cell structure. results and foamed products may be obtained by employing catalysts including or prepared from (a) prereacted organic esters of acids derived from the oxides of phosphorous plus a mineral acid, or (b) a blend of unreacted ester components such as a polyhydric alcohol and a selected acid derived from an oxide of phosphorous plus a mineral acid or (c) a blend of a prereacted organo phosphoric acid ester and one or more unreacted ester components such as a polyhydric alcohol and/or phosphoric acid, with or without a mineral acid.

A further object of the invention is to provide foaming compositions of the character mentioned incorporating a phosphatide which improves the physical strength characteristics of the cellular products. The inclusion of a selected proportion of the phosphatide in the re actant. foaming mixture has been found to regulate or adjust the wall thickness of the cells of the foam to the.

end that the cells are somewhat larger in size, more uniform in size and have greater wall thickness so that the foamed or cellular product has greater uniformity and superior physical strength characteristics.

Other objects and features of the present invention will become apparent to those skilled in the art from the following detailed description.

In preparing the cellular or foamed plastic. materials.

of the invention we employ an acid catalyzable water miscible phenolaldehyde resol, a gassing agent and a special acid catalyst. i

The phenol-aldehyde resol or. resols employed in the l reactant foaming compositions of the invention are pri=. ma'rily derived from the reactionof phenols and alde compound, an aldehyde and an alkaline catalyst. The" following are illustrative formulations of phenol-aldehyde resols suitable for incorporation in the reactant mixtures or compositions of the invention:

RESIN 1 Phenol 1 mol. Formaldehyde 1 to 2.5 m'0ls. Barium hydroxide 8I-Is0 0.003 to 0.02Qmola RESIN 2- Para-isopropyl phenol 1 mol.

Formaldehyde 1 to 2.5 mols. Calclum carbonate 0.003 to 0.020 11101.

We have found that identical or comparablev *IiESINe P Ill-235761 1 mol total the parachloro phenol Parachlol'o Phenol "ing in the proportion of from 5t0 75% by 11101 weight).

Polyvinyl'al'cohole 1 'to 1 5% ib kvei nt of the total weight of the ph'enol--and:formh e yde v. Barinm hydroxide 8HZO 0.003 to 0.020 mol.

R ES'IN 7 lihe nolL 1m I-.- Ftlrfural; 1 to 2.5 iujols total (the furfurzil Forma1dehyde; being inthe proportion of from 5 to 50% by inol weight). Polyvinyl alcohol 5 to 50 grams. Barinnr'hyd1'oxide8H20u 0.003 to- 0.020 mol.

RESIN 8 P enol, 1 mol total (the resorcino1 being Resor'cinol in the proportion of from 5 to .75%.by'mo1weight). Formald hyde 1, to.2.5 mole Barium hydroxide 81 120-- 0.003-to-0.020 mol. Polyvinylalcohol a. 1. to,15% by weight of the com- .bined ,weight of the other components.

The formaldehyde used in pr'epar'in'g'the above phenolaldhyde resols is p'referfaljlyin the form of an aqueous solution having aformaldehyde concentration of from 30 to40% by weig'ht and usually about'37% byweight. In prep aring' the "reactant mixtures or formulations of the invention the phenol-aldehyde "resols,such as above described, may be used separately or in selected blends or mixtures. The phenol aldehyde resol or the blend thereof is used" in the proportionof from about 60% to about 90% by 'Weightof the total reactant mixture.

The gassingagent or agents used in preparing the cellular phenolic productsar'e preferably metals, such as aluminum, zinc, iron or magnesium in divided form or may "be Water soluble substances that will evolve gas while in contact with the Water soluble acidic part of the catalyst, to be described below. Aluminum, zinc, iron'or inagnes'iump'referably in atomized form of from 600 'to 200 mesh employed individuallyor in suitable mixtures are effective as gassing agents as are'these' metals in thefori'n' "ofleafiiigp'owders of the same or comparable Ifish. -Sodium bicarbonate, potassium bicarbonate, lithiiiirr bic arboiiate, sodium carbonate, potassium carbonate, lithiuin carbonate, ammonium carbonate, sodium nitrite, potassiumnitrite, and the like, may be used as the'gassing agentin place of the 'divide'd metal orme'tals enumerated above. 'It is usually 'pr'e'fer'red to employ the desired or selected divided metator'co'mbinanon of metals as'they havebeen found to produce superior results. The gassing agent'is used in theformulations' ofthe invention in the proportion of from 0.2 to 10% by Weight of the total mixture.

, We have discovered that modifiers-in the form of ester phosphatides impart desirable physicalcharacteristics to the products of the invention. These additives or modifiers increase the physical "strength of the cellular products and aid'in obtaining uniform cell structures. The

ester phosphaitides assist'in controlling the initialfoaming ratej'p'rodiie somewhat -larger cells and by regulating the cell wall thickness of thefoam assure a physically stronger product. The ester phosphatides include lecithin and cephalinfiteph'alin) 'iiiid' arensed' in'tlie 'proport-ion' of from A5 to 10% and preferably /2 to 5% by Weight 'ofthctotal mixture;

The catalysts of the invention are mixtures or blends of acids in aqueous solutions. The acids of the blends are 1) acids derived from the oxides of phosphorous and their organic esters and (2) selected mineral acids or unsubstituted acids of oXide's'ofphosphorous. In addition the catalysts include certain selected diluent-s and water, the water preferably occurring as the carrier for the dilii'e'nts th'em'selv'esan'd/ or the acids. The "catalysts are characterized in "part by "allt'yl or "ar'yl-"o'r alkfaryl esters of certain classes of phosphoric acids. The alkyl and arylfr- 'g'roups act as modifying'agentsfor tlrepho'sphoric acid and may be represented its-follows:

omit-h n or greater thanl andw'here R represents:

(d) Alhybgroups from'met-hyl tostearyl and preferably 'from methyl to lauryl and except for methyl having:

-'Exar1iples of these modified organo phosphoric acids are:

. Glycero phosphoric acid Di-methyl-acid pyrophosphate Mono-octyl-acid-pyrophosphate -Di-methyl-tri-polyphosphoric acid Mono-o'ctyl-hemi phosphoric acid Mono-ethyl-di-meta-phosphoric acid where thephenylgroup is substituted-for the-octyl, methyl or ethyl group.

The'mirieral acids an'd t'uisubstituted acids that are blended or mixed with t'he organo phosphoric acids above described i'ncl'tidehydrochloric acid, sulfuric acid, phosphor'ic-acid'a nd hydrates of phosphorousoxides. The relativep'ropor'tionsor'ratios of the organo phosphoric acids'to the"'rniner-al acids or unsubstituted phosphoric acids will, of course, depend upon the strengths or conce'ntrations of a the T aqueous acid solutions and upon the particular raanrin pnenolicresin formulations in which they are to be employed. In general, the rat'iofrange' in percent'hywei g htis between l0- and 90%"of' thernin'eral or'u'ns'ubstitutedacid to betWeen90'a'nd 10% of the organo phosphoricacid. The oxy acidsof phosphorous and their partial organic-esters, which We have sometimes referred to a'sthe rg'ano phosphoric acids, serve to control or slow ddwnthe rate ofreaction of the reactant phenol aldehyde foaming miXtures While the mineral acids or unsubstituted phosphoric-acids tend to produce a rather r'ap'id 'r'eact'ionbut a greater degree of cure. Accordingly, ther'atios-or relative proportions of the acids inay be selected or chosen to obtain the rate of reaction best suited for the particular foaming phenol-aldehyde mixture and forthe particular use or application of the same.

"The abovenientioned diluents for the acid blend catalysts may be glycerol, di-alkylene'glycols, polyethylene-or polypropyleneglycols. These diluen'ts serve to assist in controllingt'he'rate "of rise or reaction of the foaming phenol-aldehyde"miXtures-and may be used in theproportion o'f fro'mfs to by weight of the total catalyst mixture, de ending upon the ceneentration or: strength'of Any of the above modified organophosphoric-acids the aqueous carrier and upon the type of phenol-aldehyde resin reactant mixture. The remainder or balance of the catalyst is water which in practice is in the proportion of from to 60% by weight of the total catalyst mixture. The following are typical examples of the catalysts of the invention such as above described; the proportions in these and the other examples being in percentages by weight:

Catalyst A-1 Percent Mono-ethyl-ortho-phosphoric acid 18 to Hydrochloric acid (100%) 34 to 42 Water 40 to 56 Catalyst A-2 Mono-glycero ortho-phosphoric acid 18 to 10 Phosphoric acid 5.----. 34 to 42 Water 40 to 56 Catalyst A3 Di-methyl-acid-pyrophosphate 18 to 10 Sulfuric acid 34 to 42 Water 40 to 56 The following are typical illustrative example of the reactant foaming compositions or mixtures of the invention employing or embodying catalysts such as above described:

EXAMPLE 1 Percent Resin No. 1 85 Aluminum powder 2 Catalyst A-1 13 EXAMPLE 2 Resin No. 1 83 Aluminum powder 2 Catalyst A-l 13 Lecithin 2 EXAMPLE 3 Resin N0. 7 M 85 Aluminum powder 2 Catalyst A-2 13 In Examples 1, 2 and 3 the ratio of resin to catalyst may range between 65% by weight of the resin to 35% by Weight of the catalyst and 90% by weight of the resin to 10% by weight of the catalyst.

As previously described or mentioned, we have found that unreacted ester components may be blended or mixed with the prereacted esters or partial esters of polyhydric alcohols and acids of anhydro bases of phosphorous to constitute catalysts which are comparable to or substantially identical with the above described catalysts when employed in the reactant resol-type of phenolic resin mixtures. The following are examples of such catalysts:

Catalyst B-I Percent EXAMPLE 4 Percent Resin No. 1 Aluminum powder 2 Catalyst B-l p 18 XAMPLE 5 Resin No. 1

Aluminum powder -t. 2 Catalyst B-l 12 Cephalin 1 EXAMPLE 6 Resin No. 7 80 Zinc powder 3 Catalyst B-2 17 EXAMPLE 7 Resin No. 6 75 Aluminum powder 3 Catalyst B3 20 Lecithin 2 EXAMPLE 8 Resin No. 1 50 Resin No. 6 26 Aluminum powder 2 Catalyst B-3 22 We have also found that catalysts containing unreacted ester components in conjunction with the mineral acids serve in the reactant foaming phenolic resin mixtures in the same manner as the earlier described catalysts. The following are examples of this class of catalysts of the invention:

Catalyst C-1 Percent Glycerol 20 Ortho-phosphoric acid (100% 10 to 20 Water 30 to 50 Hydrochloric acid (100%) 30 to 20 Catalyst C-2 Percent Diethylene glycol 20 Orthophosphoric acid (100%) 10 to 20 Water 30 to 50 Hydrochloric acid 100%) 30 to 20 The following are illustrative examples of the foaming reactant phenolic resin compositions of the invention incorporating catalysts of this type:

In Examples 4 to 11 inclusive, the ratio of the resin to the catalyst may range between 65 by weight of the resin-to 35% by weight of the catalyst and by weight of the resin to 10% by weight of the catalyst.

In preparing the cellular phenolic resin products of the,

invention the-selected-catalyst isprepared as one package? and the resin or resol(s) forms the other package.

Where an ester phosphatide is to be used it is preferably inco po a ed i he c alys as in ca ed above- T gassing agent and any additives or fillersiare also :prefer ably incorporated in the resin package. When it is desired to prepare and apply or pour the foamed product the packages just described are thoroughly mixed together and the resultant reactant mixture ,is then applied by pouring, brushing, blading, dipping, or the like. The mixture foams and reacts at atmospheric pressure and room temperature to produce the cellular product, the reactionbeing accompanied. by. exothermic heat which .sets the .foam ..or cellular mass. The .product may be post cured for several hours at a slightly elevated temperature, say at astemperatureof from 150 F. to 250 F.

It should be understood that the invention is not to be based upon or dependent upon the theories which we have expressed. Noris the invention to be regarded as limited to the express procedure or material set forth, these detailsbeing given onlyby way of illustration and to aid in clarifying the invention. We do not regard such Specifiedetailsas essential to the invention except insof as they are expressed by wayof limitation in the following claims in which it is our invention to claim all novelty inherent in the invention as broadly .as is permissible in view of the prior art.

We claim:

1. The cellular plastic material which is the product of reaction of a foaming fiowable composition comprising on a percentage by weight basis from about 60 to about'90% of an acid catalyzable water miscible phenolaldehyde resol, from about 0.2 toabout 10% of a water insoluble; gassing agent that liberates gas when reacted with .an acid selected from the group of metallic powders consisting of aluminum powder, zinc powder, iron powder andmagnesium powder, and acatalyst comprising from 10 to 18% of an organo phosphoric acid selected from the group consisting of-glycero phosphoric acid, .di-methyl-acid-pyrophosphate, mono octyl acidpyrophosphate, ,di:methyl-tri=polyphosphoric acid, monooctylhemi phosphoric acid, mono-ethyl-di-meta-phosphoricacid; a mineral acid in the proportion of from 10 to 9 %t and from 90 to 10% of the organo phosphoric acid, from to 60% water, and from 5 to 50% by weight of the catalyst of a polyhydric alcohol the catalyst being in :the proportion range of from 35% of the catalyst to 65% of the resin to of the catalyst to 90% of the resin.

2. The cellular plastic material which is the product of reaction of a foaming fiowable composition comprising; on a percentage by weight basis from about 60 to about 9.0% of an acid catalyzable water miscible phenolaldehyde resol, from about 0.2 to about 10% of a water .insoluble gassing agent that liberates gas when reacted with an acid selected from the group of metallic powders consisting of aluminum powder, zinc powder, iron powder and magnesium powder, and a catalyst comprising from 10 to 18% ofan organo phosphoric acid selected from the group consisting of-glycero phosphoric acid, di-methyl-acid-pyrophosphate, mono octyl acidpyropho-sphate, di-methyl-tri polyphosphoric acid, monooctyl hemi phosphoric acid, mono-ethyl di-meta-phosphoric acid; an oxy acid of phosphorous in the propor:

tion of from 10 to 90% and from 90 to 1 0 of the.

organo phosphoric acid and from 5 to 60% water, the catalyst being in the proportion range of from 35%. of the catalyst .to. 65% of the resin-to 10% of the catalyst to 90% .of the resin.

3. The cellular plastic material which is the product ofreaction of a foaming fiowable composition comprising on; a percentage by. weight basis from about 60 to about-90% of acid catalyzable water miscible phenolaldehyden-resol, ,f-romabou-t 0.2 toabout 10% of a water insoluble gassing agentthat liberates gaswhen-- reacted with an acid selected fromthe group ofmetallic powders. consisting -of aluminum powder, zinc' powder, iron powder andmagnesium powder, and a catalyst comprising from 1.0 to 18% of an organo phosphoric acid selected from the group consistingof glycero phosphoric acid, -di-methyl-acid-pyrophosphate, mono octyl acidpyrophosphate, diemethyl-tri-p lyphosphoric acid, monooctyl-hemi-phosphoric acid, mono-ethyl-di-meta-phosphoric acid; a mineral acid in the proportion ratio'of from 10 to 90% and from 90 to 10% of the organo phosphoric acid, and about 5 to 60% water, the catalyst being in the proportion range of from of the catalyst to 65% of the resin to 10% of the catalyst to 90% of the resin.

4. The cellular plastic material which is the product of reaction of a foaming fiowable composition on a percentage by weight basis from about to about 90% of an acid catalyzable water miscible phenol-aldehyde resol, from about 0.2 to about 10%, of a water insoluble gassing agent that liberates gas when reacted with an acid selected from the group of metallic powders consisting of aluminum powder, zinc powder, iron powder and magnesium powder, and a catalyst comprising from 10 to 18% of an organo phosphoric acid selected from the group consisting of glycero phosphoric acid, di-methylacid-pyrophosphate, mono-octyl-acid-pyrophosphate, dimethyl-tri-polyphosphoric acid, mono-octyl-hemi-phosphoric acid, mono-ethyl-di-meta-phosphoric acid; an acid selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid and hydrates of phosphorous oxides in the proportion of from 10 to 90% and 90 to 10% of the organo phosphoric acid and from. about 5 to 60% water, the catalyst being in the proportion range of from 35% of the catalyst to of the resin to 10% of the catalyst to of the resin.

5. The cellular plastic material which is the product of reaction of a foaming fiowable composition compris-' ing on a percentage by weight basis from about 60 to about-90% of an acid catalyzable water miscible phenol aldehyde resol, from about 0.2 to about 10% of a water insoluble gassing agent that liberates gas when reacted with an acid selected from the group consisting of aluminum powder, zinc powder, iron powder and magnesium powder, and a catalyst comprisingfrom 10 to 18% of an organo phosphoric acid selected from the group consisting of: glycero phosphoric acid, di-methyl-acidpyrophosphate, mono-octyl-acid pyrophosphate, di-methyltri-polyphosphoric acid, mono-octyl hemi phosphoric acid, mono-ethyl-di-meta-phosphoric acid;-an acid selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid and hydrates of phosphorous oxides in the proportion of from 10 to 90% and from 90 to 10% of the organo phosphoric acid, and from about 5 to.60% water, the catalyst being .in the proportion range of from 35% of thecatal'yst'to 65 of the resin to 1 0% ofthe catalyst to 90% of the resin.

6. The cellular plastic material which is the product of reaction of a foaming fiowable composition comprising on a percentage by weight basis from about 60 to 90% of, an acid catalyzable water miscible phenol-aldehyde resol, from about 0.2 to about 10% of a water insoluble gassing agent that liberates gas when reacted with an acid selected fromthe group. of metallic powders consisting of aluminum powder, Zinc powder, iron powder and magnesium powder, and a catalyst comprising from 10 to 18% of an organo phosphoric acid selected from the group consistingofglycerophosphoric acid, di-rnethyl acid pyrophosphate, monofoctyl-acidpyrophosphate, di-methybtripolyphosphoric. acid, monooctyl hemi phosphoric acid, mono-ethyl-dimeta-phosphoric acid; an oxy acid of phosphorous in the proportion of from 10 to 90% .andfrorn .90. to. 10 %-,of.;th'e organophosphoric acid, from 5 to 50% by weight-of the catalyst of a polyhydric alcohol. and' fromyahol itfi to 60% water, the catalyst being in the proportion range 9 of from 35% of the catalyst to 65% of the resin to 10% of the catalyst to 90% of the resin.

7. The cellular plastic material which is the product of reaction of a foaming composition comprising on a percentage by weight basis about 85% of an acid catalyzable water miscible phenol aldehyde resol, about 2% aluminum powder, and about 13% of a catalyst comprising from 18 to 10% mono-ethyl-ortho-phosphoric acid, from 34 to 42% hydrochloric acid and from 40 to 56% water.

8. The cellular plastic material which is the product of reaction of a foaming composition comprising on a percentage by weight basis about 83% of an acid catalyzable water miscible phenol-aldehyde resol, about 2% aluminum powder, about 2% lecithin, and about 13% of a catalyst comprising from about 18 to 10% monoethyl-ortho-phosphoric acid, about 34 to 42% hydrochloric acid, and about 40 to 56% water.

9. The cellular plastic material which is the product of reaction of a foaming composition comprising on a percentage by weight basis about 80% of an acid catalyzable water miscible phenol-aldehyde resol, about 2% aluminum powder and about 18% of a catalyst comprising from about 10 to 14% mono-octy1-acid pyrophosphate, from about 18 to 14% phosphoric acid, about 44% glycerol, and from about 24 to 32% water.

10. The cellular plastic material which is the product of reaction of a foaming flowable composition comprising on a percentage by weight basis from about 60 to about 90% of an acid catalyzable water miscible phenolaldehyde resol, from about 0.2 to about 10% of a water insoluble gassing agent that liberates gas when reacted with an acid selected from the group of metallic powders consisting of aluminum powder, Zinc powder, iron powder and magnesium powder, from about /8 to 10% of an ester phosphati-de selected from the group consisting of lecithin and cephalin and a catalyst comprising from 10 to 18% of an organo phosphoric acid selected from the group consisting of glycero phosphoric acid, di-methylacid-pyrophosphate, mono-octyl-acid-pyrophosphate, dimethyl-tri-polyphsphoric acid, mono-octyl-hemi-phosphoric acid, mon-ethyl-di-meta-pho-sphoric acid; a mineral acid in the proportion ratio of from 10 to 90% and from 90 to 10% of the organo phosphoric acid, and about to 60% water, the catalyst being in the proportion range of from 35% of the catalyst to 65 of the resin to of the catalyst to 90% of the resin.

11. The cellular plastic material which is the product of reaction of a foaming flowable composition comprising on a percentage by weight basis from about 60 to 90% of an acid catalyzable water miscible phenol-aldehyde resol, from about 0.2 to about 10% of a water insoluble gassing agent that liberates gas when reacted with an acid selected from the group consisting of aluminum powder, zinc powder, iron powder and magnesium powder, from about /s to 10% of an ester phosphatide selected from the group consisting of lecithin and cephalin, and a catalyst comprising from 10 to 18% of an organo phosphoric acid selected from the group consisting of: glycero phosphoric acid, di-methyl-acid-pyrophosphate, monooctylacid-pyrophosphate, di-methyl-tri-polyphosphoric acid, mono-octyl-hemi-phosphoric acid, mono-ethyl-di-metaphosphoric acid; an oxy acid of phosphorous in the mo portion of from 10 to 90% and from 90 to 10% of the organo phosphoric acid, from 5 to 50% by weight of the catalyst of a polyhydric alcohol and from about 5 to 60% 10 water, the catalyst being in the proportion range of from 35% of the catalyst to 65 of the resin to 10% of the catalyst to of the resin.

12. The cellular plastic material which is the product of reaction of the foaming composition comprising on an approximate percentage by weight basis from 60 to 90% of an acid catalyzable water miscible phenol-aldehyde resol, from 0.2 to 10% of a water insoluble gassing agent that liberates gas when reacted with an acid selected from the group consisting of aluminum powder, zinc powder, iron powder and magnesium powder, and a catalyst in the proportion range of from 35% of the catalyst to 65% of the resin to 10% of the catalyst to 90% of the resin, the catalyst comprising from 10 to 14% mono-octyl-acid pyrophosphate, from 18 to 14% phosphoric acid, about 44% glycerol and from 24 to 32% water.

13. The cellular plastic material which is the product of reaction of the foaming composition comprising on an approximate percentage by weight basis from 60 to 90% of an acid catalyzable water miscible phenol-aldehyde resol, from 0.2 to 10% of a water insoluble gassing agent that liberates gas when reacted with an acid selected from the group consisting of aluminum powder, zinc powder, iron powder and magnesium powder, from A; to 10% of an ester phosphatide selected from the group consisting of lecithin and cephalin, and a catalyst .in the proportion range of from 35% of the catalyst to 65% of the resin to 10% of the catalyst to 90% of the resin, the catalyst comprising from 10 to 14% mono-octyl-acid pyrophosphate, from 18 to 14% phosphoric acid, about 44% glycerol and from 24 to 32% water.

14. The cellular plastic material which is the product of reaction of a foaming flowable composition comprising on a percentage by weight basis from. about 60 to 90% of an acid catalyzable water miscible phenolaldehyde resol, from about 0.2 to about 10% of a Water insoluble gassing agent that liberates gas when reacted with an acid selected from the group consisting of aluminum powder, Zinc powder, iron powder and magnesium powder, from about A; to 10% of lecithin, and a catalyst comprising from 10 to 18% of an organo phosphoric acid selected from the group consisting of: glycero phosphoric acid, di-methyl-acid-pyrophosphate, mono-octyl-acid-pyrophosphate, di-methyl-tri-polyphosphoric acid, mono-octylhemi phosphoric acid, mono-ethyl-dhmeta-phosphoric acid; an oxy acid of phosphorous .in the proportion of from 10 to 90% and from 90 to 10% of the organo phosphoric acid, from 5 to 50% by Weight of the catalyst of a polyhydric alcohol and from about 5 to 60% water, the catalyst being in the proportion range of from 35% of the catalyst to 65 of the resin to 1.0% of the catalyst to 90% of the resin.

References Cited in the file of this patent UNITED STATES PATENTS 2,272,847 Macht Feb. 10, 1942 2,398,703 Gardner M Apr. 16, 1946 2,446,429 Nelson et al Aug. 3, 1948 2,529,512 Ott Nov. 14, 1950 2,544,483 Baum Mar. 6, 1951 2,582,228 Brinkema Jan. 15, 1952 2,653,139 Sterling Sept. 22, 1953 FOREIGN PATENTS 410,200 Canada Jan. 26, 1943 

1. THE CELLULAR PLASTIC MATERIAL WHICH IS THE PRODUCT OF REACTION OF A FOAMING FLOWABLE COMPOSITION COMPRISING ON A PERCENTAGE BY WEIGHT BASIS FROM ABOUT 60 TO ABOUT 90% OF AN ACID CATALYZABLE WATER MISCIBLE PHENOLALDEHYDE RESOL, FROM ABOUT 0.2 TO ABOUT 10% OF A WATER INSOLUBLE GASSING AGENT THAT LIBERATES GAS WHEN REACTED WITH AN ACID SELECTED FROM THE GROUP OF METALLIC POWDERS CONSISTING OF ALUMINUM POWDER, ZINC POWDER, IRON POWDER AND MAGNESIUM POWDER, AND A CATALYST COMPRISING FROM 10 TO 18% OF AN ORGANO PHOSPHORIC ACID SELECTED FROM THE GROUP CONSISTING OF -GLYCERO PHOSPHORIC ACID, DI-METHYL-ACID-PYROPHOSPHATE, MONO-OCTYL-ACIDPYROPHOSPHATE, DI-METHYL-TRI-POLYPHOSPHORIC ACID, MONOOCTYL-HEMI-PHOSPHORIC ACID, MONO-ETHYL-DI-META-PHOSPHORIC ACID; A MINERAL ACID IN THE PROPORTION OF FROM 10 TO 90% AND FROM 90 TO 10% OF THE ORGANO PHOSPHORIC ACID, FROM 5 TO 60% WATER, AND FROM 5 TO 50% BY WEIGHT OF THE CATALYST OF A POLYHDRIC ALCOHOL THE CATALYST BEING IN THE PROPORTION RANGE OF FROM 35% OF THE CATALYST TO 65% OF THE RESIN TO 10% OF THE CATALYST TO 90% OF THE RESIN. 